Colored hair lacquers and hair setting compositions



United States Patent COLORED HAIR LACQUERS AND HAIR SETTING COMPOSITIONS ErwinHahn, Viernheim, Guenter Lange and Wolfgang .6 Claims. (61. 16788) This invention relates to hair lacquers and hair setting compositions which at the same time 'dye or tint the hair.

Colorless hair lacquers and hair setting compositions are known in which natural or synthetic macromolecular substances serve as lacquer base materials. Hair lacquers and hair setting compositions arealso known which contain soluble dyes for dyeing or tinting the hair. The dye mayhowever bleed from the lacquer films produced on the hair with prior art agents. Particularly when wetted with water, when atmospheric humidity is high or *by perspiration, hair thus treated may stain the facefor clothing or linen ,which comes into contact withthe hair.

It is an object of the present invention to provide colored hair lacquers and hair setting compositions from which the dye does not bleed, so that the hair is not dyed directly. Another object is colored hair lacquers and hair setting compositions which can be removedfrom the hair by simple washing. A further object is colored hair lacquers and hair setting compositions which do not produce a lasting dyeing effect on other objects, for example when carelessly handled.

We have now found that hair lacquers and hair setting compositions in which the dye is covalently combined with or built into the macromolecular'substance serving as the lacquer base material or a macromolecular substance with which the lacquer base material is compatible, impart well fixed tints to the hair from which the dye does not bleed.

Colored hair lacquers and hair-setting compositions according to this invention are obtainable for example from polymers containing reactive groups and dyes also containing reactive groups, or by copolymerizationof .wholly or partly saponified. Dyes which contain reactive groups are chemically combined withthese polymers by chemical reactions, particularly by condensation reactions.

Dyes suitable 'for this purpose are for example those of the azo or anthraquinone. series containing N-methylol groups-as the reactive groups.

The following are examples of dyes-whichcan be combined with polymers. by condensation: the coupling product of diazotized N-(p-aminophenyl)rglyoxal-diureine .and 1 (p sulfophenyl) 3 -,meth'ylpyrazolone-(5) which has been reacted with formaldehyde; the coupling product of diazotized N-(p-aminophenyl)-glyoxaldiureine and N acetylaminonaphthol-(l)-3,6 disulfonic acid which has been reacted with formaldehyde; the coupling product of diazotized N-p-aminophenylurea and 4-tertiary-butylphenol which. has been reacted WithfQrmaldehyde; and 4-azophenylacetoaceticacid anilide.

acrylic esters and vinyl esters and colorless Patented May .17, 1966 Examples of colored polymers are copolymers of acrylamide, methacrylamide, low molecular weight acrylic esters, low molecular weight methacrylic esters, vinyl acetate, vinyl propionate and especially of vinyl lactams such as N-vinylpyrrolidone with dyes having a polymerizable olefinic'group outside the chromophoric system. The general production of such polymers and also a number of copolymerizable dyes may be seen inter alia in US-patent-application Serial No. 105,267, filed April 25, 1961, by Guenter Lange, Guenther Krehbiel, Hans Wilhelm, Ernst Penning, Gerd Louis, and Hans Weidinger, now abandoned in favor of pending continuation-in-part application Serial No. 344,082, filed February As dyes which can be used for copolymerization the following are suitable for example: the coupling products of l-amino-3-acryloylaminobenzene with 1-[N-(2-hydroxyethyl) N (2 cyanoethyl) amino] 3 methylbenzene, of l amino 4 acryloylaminobenzene with 1- hydroxynaphthalene 4 sulfonic acid, of 2,4 dichloraniline with N ethyl -N ,9 vinyloxyethylaniline, of p aminostyrene with -1 hydroxynaphthalene 4 sulfonic acid and l-amino 2 acetyl 4 acryloylaminoanthraquinone.

By appropriate choice of the initial monomers, the dyes and the relative proportions, it is possible for an expert to prepare lacquers which fulfil the special requirements of hair lacquers or hair setting compositions.

Having regard tothe purpose, the most suitable-dyes are yellow, red, blue and brown dyes, but other dyes may also be used to achieve fashionable effects. It is very advantageous to make up the desired shade in each case by mixing hair lacquers of only a few standard colors.

Besides mixtures of difierently colored macromolecular substances, mixtures of colored macromolecular substances and colorless macromolecular substances may he used with good results. Especially suitable aremixtures of colored polymers on the basis of N-vinylpyrrolidone, polymers from the said monomers.

The proportion of dye in the polymer may be between 0.1 and 5% by Weight depending on whether the hair lacquer is mainly for dyeing or only tinting the hair.

The' proportion of dye may if-desired be as-high asnp to 25% or more if the polymer is to be used as a component for mixing with colorless hair lacquer, for example hair lacquer based on polymers, polycondensates or natural lacquer base materials, such as shellac.

By combination of the dye with or by building. the dye into the polymeric lacquer base material, the mechanical properties and also the'afiinity'for solvents and water are in general only altered trivially. If necessary, any .un-

desirable changes in properties, for. example slight embrittlement, may be compensated for without difiiculty by means of internally plasticising comonomers, such as 'butyl acrylate, or by adding conventioinal plasticisers.

The colored hair'lacquers and hair setting compositions maybe used as hairsprays or as aqueous and/or aqueous-alcoholic solutions (frictions) for massaging into the hair. Coloredhair lacquers to'be used as sprays are suitable chiefly for-tinting the hair because they merely coatthe hair superficially. On'the other-hand,-the hair The advantages of the colored hair lacquers and hair setting compositions according to the invention are that hair may be conveniently tinted or dyed at the same time as it is being set, that the dye cannot bleed out from the lacquer film and cause staining, and thatthe colored lacquer may be removed justas easily as colorless lacquer without traces of the dye remaining on the hair. When washing out, there is no risk of undesirable staining because the vcolored lacquer. substance has no aflinity. Finally, the convenient washing out of the lacquer makes it possible, as is often desired, to impart a special tint to the hair for only a short time.

The following examples further illustrate, but do not limit, the invention. The parts and percentages are by weight.

Example I Example 2 A 24.2% polymer solution is prepared from 75 parts vinylpyrrolidone, 20 parts acrylamide, parts of the dye specified in Example 1 and 1 part azodiisobutyronitrile by solution polymerization in 300 parts of water.

This solution, after dilution in the ratio 1:7 with Water and the addition of perfume, is suitable as a liquid hair.

setting composition for blond tinting of hair.

Example 3 A 23.2% polymer solution is prepared from 75 parts vinylpyrrolidone, 15 parts acrylamide, 5 parts vinyl acetate, 5 parts of the dye specified in Example 1 and 2 parts azodiisobutyronitrile by solution polymerization in 300 parts of a mixture of ethanol and water in the ratio 35:65. This solution, when diluted in the ratio 1:7 with the mixture of ethanol and water, is suitable as a liquid hair setting composition for blond tinting of hair.

Example 4 15 parts of a red dye prepared from diazotized N-(paminophenyl)-glyoxaldiureine and 1-naphthol-4-sulfonic acid and reacted with 3 moles formaldehyde is heated in the presence of 0.5 part ammonium nitrate with 35 parts polymethacrylamide suspended in 200 parts glycol monomethyl ether at 122 C., a macromolecular dye thus being formed.

2 parts of this dye is mixed with 98 parts polyvinyl alcohol. This mixture may be used in the form of a 3% aqueous solution as a hair setting composition for red blond tinting of hair.

Example 5 1 part of the macromolecular dye described in Example 4 is mixed with 99 parts of a solution polymer obtained from 60 parts vinyl pymrolidone, 32.5 parts vinyl acetate and 7.5 parts acrylamide. This mixture may be used in the form of a 3% solution in a mixture of ethanol End water in the ratio 35:66 for red blond tinting of air.

Example 6 Hair spray preparations are made in conventional manner from equal'amounts of colored polymer solutions, the production of which is described below, and a propellant consisting of 1 part trichlorofluoromethane and 9 parts dichlorodifiuoromethane while coemploying perfume and 0.8% polyethylene glycol ether as plasticizer.

4 The preparations are used for setting hair and tinting it (a) red blond, (b) red violet, (0) red orange, (d) brown red, (e) carmine red and (f) purple shades.

The hair lacquers are clear and tack-free and give an immaculate set to the coitfure. They can be easily removed by washing the hair.

Liquid settingcompositions for massaging into the hair can be prepared from the same polymers in conventional manner, for example, from 5% of the colored polymer, 50% isopropanol, small amounts of penfume, hair-preparations and plasticizer with the balance water. By using liquid hair setting composition, the hair is dyed a fuller shade.

The polymer solutions are prepared as follows:

A solution of 7.5 parts vinylpyrrolidone (I), 10 parts vinyl acetate (II), 10 parts ethyl acrylate (III), 0.5 part azodiisobutyronitrile (IV), 0.1 part sodium hydrogen sulfite (V), 1 part water (VI) and 30 parts acetone (VII) is heated to 70 C. Over a period of 20 minutes, a solution of 15 parts I, 15 partsII, 10 parts III, 0.25 part IV, 0.1 part V, 1 part VI, and 30 parts VII is added and thereafter, again over a period of 20 minutes, a solution of 10 parts I, 5 parts II, 10 parts III, 0.25 part IV, 0.1 part V, 1 part VI, 40 parts VII and 7.5 parts of a polymerizable azo dye prepared by coupling (a) Diazotized 2-cyano-4-nit-raniline and N-ethyl-N- (acryloyloxyethyl aniline;

(b) Diazotized 2-trifluoromethyl-4-nitraniline and N- The colored polymer may also be produced by precipitation, by using for the initial monomer solution 300 parts of water instead of 1 part andrunning in'a monomer mixture of the said composition dissolved in 600 parts wateri 1 Example 7 A spray preparation for the simultaneous setting and.

blond tinting of hair is prepared from-40 parts of a 3% yellow polymer solution in ethanol, the production of which is described below, and parts of a propellant consisting of equal parts of trichlorofluoromethane and dichlorodifluoromethane.

The polymer solution is prepared as follows: A solution of 15 parts vinylpyrrolidone (I), 10 parts vinyl acetate (II), 10 parts ethyl acrylate (1H), 0.25 part azodiisobutyronitrile (IV), 0.1 part sodium hydrogen sulchloroaniline and N-ethyl-N-(acryloyloxyethyl)aniline is added. The whole is heated at C. for another 5 hours, the polymer precipitated by dripping slowly into ten times the amount of water and the product worked up in conventional manner.

Example 8 Aqueous hair setting compositions or spray preparations are prepared in conventional manner from 20% solid substance of each of the colored polymers described in the foregoing examples and 80% of a colorless hair lacquer prepared by one of the specifications (a) to (c).

The preparations from base material obtainable according to (a) give soft and supple films on the hair, those prepared according to (b) films of medium rigidity, and those according to (c) rigid films which are very true to shape.

The colored lacquer susbtances can be easily blended. Forexample by combination of dye (f) from Example 6 with the dye from Example 7, a brown shade is achieved.

The colorless polymers are obtained as follows (the brackets indicating the amounts to be used for specifications (b) and (c)): 5 (5; 10) parts vinylpyrrolidone, 10 (10; 10) parts vinyl acetate, (20; 10) parts ethyl acrylate and 0.25 (0.5; 0.25) part azodiisobutyronitrile are dissolved in 30 parts isopropanol and the solution is heated to 80 C. under nitrogen while stirring. Over a period of 30 (60; 30) minutes, a solution of 15 (10; parts vinylpyrrolidone, 20 (20; 20) parts vinyl acetate, (30; 20) parts ethyl acrylate,'0 (5; 0) part methyl methacrylate, 0 (0; 5) part acrylonitrile, 0.5 (1; 5) part azodiisobutyronitrile and 70 parts isopropanol.

Polymerization is completed within 8 hours and the polymer worked up in the usual manner.

We claim:

1. A hair coloring composition for application to hair comprising a liquid solvent selected from the group consisting of Water, ethanol, isopropanol and mixtures thereof and, as a coloring ingredient dissolved in said liquid solvent, about 0.03% to 5%, based on said composition, of a soluble addition polymer of (a) 75 to 99.9% by weight of at least one colorless, olefinically-unsaturated monomer selected from the group consisting of acrylamide, methacrylamide, acrylic and methacrylic acid esters of a lower a1- kanol, vinyl acetate, vinyl propionate and N-vinylpyrrolidone, and

(b) 0.1 to 25% by weight of a colored monomer selected from the group consisting of anthraquinone azo dyes embodying acryloyl groups,

said monomers (a) and (b) being polymerized in said addition polymer through the olefinic groups thereof.

2. A hair spray preparation for the simultaneous tinting and setting of hair consisting essentially of propellant, a solvent selected from the group consisting of water, ethanol and isopropanol and, as a coloring ingredient dissolved in said solvent, about 0.03% to 5 based on said composition, of a soluble addition polymer of (a) 76 to 99.9% by weight of at least one colorless, olefinically unsaturated monomer selected from the group consisting of acrylamide, methacrylamide, acrylic and methacrylic acid esters of a lower alkanol, vinyl acetate, vinyl propionate and n-vinylpyrrolidone, and

(b) 0.1 to 25% by weight of a colored monomer selected from the group consisting of anthraquinone and azo dyes embodying acryloyl groups,

said monomers (a) and (b) being polymerized in said addition polymer through the olefinic groups thereof.

3. A composition as claimed in claim 1 wherein said dye is diazotized N-acryloyl-p-phenyl diamine coupled with 1-(2-chloro-5-sulfophenyl-3-methylpyrazolone- (5) 4. A composition as claimed in claim 2 wherein said dye is diazotized N-acryloyl-p-phenyl diamine coupled with 1-(2-chloro-5-sulfophenyl-3-methylpyrazolone-(5) 5. A hair coloring composition for application to hair comprising a liquid solvent selected from the group consisting of water, ethanol, isopropanol and mixtures thereof and, as a coloring ingredient dissolved in said liquid solvent, about 0.3% to 5 based on said composition, of a soluble addition polymer selected from the group consisting of:

Y 6 (I) a soluble addition polymer of (a) 75 to 99.9% by weight of at least one colorless, olefinically unsaturated monomer selected from the group consisting of acrylamide, methacrylamide, acrylic and methacrylic acid esters of a lower alkanol, vinyl acetate, vinyl propionate and N-vinyl pyrrolidone, and (b) 0.1 to 25% by weight of a colored monomer selected from the group consisting of anthraquinone and azo dyes embodying acryloyl groups, said monomers (a) and (b) being polymerized in said addition polymer through the olefinic groups thereof; and

(II) a soluble addition polymer of 75 to 99.9% by weight of a member selected from the group consisting of polyacrylamide, polymethacrylamide, an addition polymer made up from monomers selected from the group consisting of acrylarnide and methacrylamide polymerized with monomers selected from the group of acrylic and methacrylic acid esters of a lower alkanol, vinyl acetate, vinyl propionate, N-vinylpyrrolidone and minor amounts of an unsaturated carboxylic acid, to which polymer is coupled by a condensation reaction 0.1 to 25% by weight of a dye selected from the group consisting of an anthraquinone dye and an azo dye, said dye embodying N-methylol groups.

6. A hair spray preparation for the simultaneous tinting and setting of hair consisting essentially of a propellant, a solvent selected from the group consisting of water, ethanol and isopropanol and as a coloring ingredient dissolved in said solvent, about 0.03% to 5 based on said composition, of a soluble addition polymer selected from the group consisting of:

(I) a soluble addition polymer of (a) 75 to 99.9% by weight of at least one colorless, olefinically unsaturated monomer selected from the group consisting of acrylamide, methacrylamide, acrylic and methacrylic acid esters of a lower alkanol, vinyl acetate, vinyl propionate and N-vinylpyrrolidone, and

(b) 0.1 to 25 by weight of a colored monomer selected from the group consisting of anthraquinone and azo dyes embodying acryloyl p said monomers (a) and (b) being polymerized in said addition polymer through the olefinic groups thereof; and

(II) a soluble addition polymer of 75 to 99.9% by weight of a member selected from the group consisting of polyacrylamide, polymethacrylamide, an addition polymer made up from monomers selected from the group consisting of acrylamide and methacrylamide polymerized with monomers selected from the group of acrylic and methacrylic' acid esters of a lower alkanol, vinyl acetate, vinyl propionate, N- vinylpyrrolidone and minor amounts of an unsatur-ated carboxylic acid, to which polymer is coupled by a condensation reaction 0.1 to 25% by weight of a dye selected from the group consisting of an anthraquinone dye and an azo dye, said dye embodying N-methylol groups.

References Cited by the Examiner UNITED STATES PATENTS 2,632,004 3/ 1953 Minsk et a1. 260l'52 2,732,382 1/1956 Minsk et al. 260-452 2,875,047 2/1959 Oster 96-1 15 2,994,693 8/1961 Blake et a1. 260144 2,996,381 8/1961 Oster et a1. 96l15 JULIAN S. LEVITT, Primary Examiner. JOSEPH R. LIBERMAN, Examiner. 

1. A HAIR COLORING COMPOSITION FOR APPLICATION TO HAIR COMPRISING A LIQUID SOLVENT SELECTED FROM THE GROUP CONSISTING OF WATER, ETHANOL, ISOPROPANOL AND MIXTURES THEREOF AND, AS A COLORING INGREDIENT DISSOLVED IN SAID LIQUID SOLVENT, ABOUT 0.03% TO 5% BASED ON SAID COMPOSITION, OF A SOLUBLE ADDITION POLYMER OF (A) 75 TO 99.9% BY WEIGHT OF AT LEAST ONE COLORLESS, OLEFINICALLY UNSATURATED MONOMER SELECTED FROM THE GROUP CONSISTING OF CRYLAMIDE, METHACRYLAMIDE, ACRYLIC AND METHACRYLIC ACID ESTERS OF A LOWER ALKANOL, VINYL ACETATE, VINYL PROPIONATE AND N-VINYL PYRROLIDONE, AND (B) 0.1 TO 25% BY WEIGHT OF A COLORED MONOMER SELECTED FROM THE GROUP CONSISTING OF ANTHRAQUINONE AZO DYES EMBODYING ACRYLOL GROUPS. SAID MONOMERS (A) AND (BE BEING POLYMERIZED IN SAID ADDITION POLYMER THROUGH THE OLEFINIC GROUPS THEREOF. 